Polycrystalline diamond composite compact elements and tools incorporating same

ABSTRACT

A polycrystalline diamond (PCD) composite compact element  100  comprising a substrate  130,  a PCD structure  120  bonded to the substrate  130,  and a bond material in the form of a bond layer  140  bonding the PCD structure  120  to the substrate  130;  the PCD structure  120  being thermally stable and having a mean Young&#39;s modulus of at least about 800 GPa, the PCD structure  120  having an interstitial mean free path of at least about 0.05 microns and at most about 1.5 microns; the standard deviation of the mean free path being at least about 0.05 microns and at most about 1.5 microns. Embodiments of the PCD composite compact element may be for a tool for cutting, milling, grinding, drilling, earth boring, rock drilling or other abrasive applications, such as the cutting and machining of metal.

This application claims the benefit of U.S. Provisional Application No.61/230,316, filed Jul. 31, 2009, which is incorporated herein byreference in its entirety.

FIELD

Embodiments of the invention relate to polycrystalline diamond (PCD)composite compact elements comprising a PCD structure, particularly butnot exclusively for a rock boring tool, and to tools comprising theelements.

BACKGROUND

Polycrystalline diamond (PCD) is a super-hard, also known assuperabrasive material comprising a mass of inter-grown diamond grainsand interstices between the diamond grains. PCD may be made bysubjecting an aggregated mass of diamond grains to an ultra-highpressure and temperature. A material wholly or partly filling theinterstices may be referred to as filler material. PCD may be formed inthe presence of a sintering aid such as cobalt, which is capable ofpromoting the inter-growth of diamond grains. The sintering aid may bereferred to as a solvent/catalyst material for diamond, owing to itsfunction of dissolving diamond to some extent and catalyst itsre-precipitation. A solvent/catalyst for diamond is understood be amaterial that is capable of promoting the growth of diamond or thedirect diamond-to-diamond inter-growth between diamond grains at apressure and temperature condition at which diamond is thermodynamicallystable. Consequently the interstices within the sintered PCD product maybe wholly or partially filled with residual solvent/catalyst material.PCD may be formed on a cobalt-cemented tungsten carbide substrate, whichmay provide a source of cobalt solvent/catalyst for the PCD.

PCD may be used in a wide variety of tools for cutting, machining,drilling or degrading hard or abrasive materials such as rock, metal,ceramics, composites and wood-containing materials. For example, PCDelements may be used as cutting elements on drill bits used for boringinto the earth in the oil and gas drilling industry. In many of theseapplications the temperature of the PCD material may become elevated asit engages a rock formation, workpiece or body with high energy.Unfortunately, mechanical properties of PCD such as hardness andstrength tend to deteriorate at high temperatures, largely as a resultof residual solvent/catalyst material dispersed within it.

PCT patent publication number WO9929465 discusses that drilling hardrock and dealing with high well bore temperature gradients have beenpersistent problems in the drilling industry. The then currentstate-of-the-art TSP diamond cutter attachment procedure is to brazethermally stable polycrystalline diamond (TSP diamond) to carbidesubstrates. However, TSP brazing methods using TiCuSil alloy result inan undesirable discontinuous layer of TiC adjacent to the TSP diamondsurface. Maximum strength properties are not realized unless a thincontinuous layer of reaction product forms on the TSP surface (i.e.unless wetting is complete).

U.S. Pat. No. 7,377,341 discusses that a PCD body that is substantiallyfree of the solvent catalyst material is precluded from subsequentattachment to a metallic substrate by brazing or other similar bondingoperation. The attachment of such substrates to the PCD body is highlydesired to provide a PCD compact element that can be readily adapted foruse in many desirable applications. However, it is very difficult tobond the thermally stable PCD body to conventionally used substrates.Since conventionally formed thermally stable PCD bodies are devoid of ametallic substrate, they cannot be attached to a drill bit byconventional brazing process. Rather, the use of such a thermally stablePCD body in drilling application requires that the PCD body itself bemounted to the drill bit by mechanical or interference fit duringmanufacturing of the drill bit, which is labour intensive, timeconsuming, and which does not provide a most secure method ofattachment.

U.S. Pat. No. 7,435,377 discusses that polycrystalline diamond (PCD) andother ultra-hard materials may be joined to a supporting mass by meansof brazing. However, a disadvantage of brazing is relates to concernsover potential heat damage of the PCD product, which has been a limitingfactor in the past.

U.S. Pat. No. 7,487,849 discusses that because TSP (thermally stableproduct) is made by removing cobalt from a diamond layer, attachment ofTSP to a substrate is significantly more complicated, as compared to theattachment of PDC to a substrate.

U.S. Pat. No. 7,533,740 discloses a cutting element comprising TSPmaterial bonded to a tungsten carbide substrate by brazing (this patentuses the term “TSP” as described in U.S. Pat. Nos. 7,234,550 and7,426,696, which use the term “TSP” to mean “thermally stable product”,including both partially and completely leached polycrystalline diamondcompounds).

United States patent publication number 2008/0085407 discloses asuper-abrasive compact element wherein a super-abrasive volume includinga tungsten carbide layer may be brazed, soldered, welded (includingfrictional or inertial welding), or otherwise affixed to a substrate.

There is a need for PCD composite compact elements, particularlythermally stable PCD elements, having superior mechanical properties.

SUMMARY

An embodiment of the invention provides a polycrystalline diamond (PCD)composite compact element comprising a substrate, a PCD structure bondedto the substrate, and a bond material bonding the PCD structure to thesubstrate; the PCD structure being thermally stable and having a meanYoung's modulus of at least about 800 GPa, at least about 850 GPa, or atleast 870 GPa, the PCD structure having an interstitial mean free pathof at least about 0.05 microns and at most about 1.5 microns; thestandard deviation of the mean free path being at least about 0.05microns and at most about 1.5 microns.

An embodiment of the invention provides a PCD composite compact elementcomprising a PCD structure bonded to a substrate by means of a bondmaterial; the PCD structure being thermally stable and having a meanYoung's modulus of at least about 800 GPa, at least about 850 GPa, or atleast 870 GPa, and a mean diamond grain contiguity greater than about 60percent or greater than 60.5 percent.

In one embodiment of the invention, the bond material may comprise anepoxy material for joining ceramic materials.

In one embodiment of the invention, the PCD structure may be brazed tothe substrate, the bond material being a braze alloy in the form of abraze layer between the PCD structure and the substrate.

In one embodiment of the invention, the braze alloy may have a meltingonset temperature, at which the alloy begins to melt, of at most about1,050 degrees centigrade, at most about 950 degrees centigrade, at mostabout 900 degrees centigrade or even at most about 850 degreescentigrade, and may contain at least one element selected from the groupconsisting of Ti, V, Cr, Mn, Zr, Nb, Mo, Hf, Ta, W and Re. In someembodiments, the braze alloy may contain Ti and Ag, or Ti and Cu.

An embodiment of the invention provides a PCD composite compact elementcomprising a PCD structure bonded to a substrate by means of a brazelayer comprising braze material; the PCD structure being thermallystable and containing braze material.

In some embodiments of the invention, the PCD structure may containbraze alloy material within pores, crevices or irregularities formed ata boundary of the PCD structure. In one embodiment, pores, crevices orirregularities may formed at a boundary of the PCD structure by removingfiller material from between diamond grains, such as by means of acidtreatment.

In some embodiments of the invention, the PCD structure may have a meanYoung's modulus of at least about 800 GPa, at least about 850 GPa, or atleast 870 GPa.

In one embodiment of the invention, the PCD structure may contain brazealloy material to a depth of at least about 2 microns from an interfaceor boundary, such as an interface with the braze layer or with thesubstrate. In some embodiments of the invention, the PCD structure maycontain braze material to a depth from an interface with the brazelayer, the depth being in the range from about 2 microns to about 1,000microns, in the range from about 2 microns to about 25 micron, or in therange from about 5 microns to about 15 microns. In one embodiment, thePCD structure may contain braze material substantially throughout thewhole of the PCD structure.

In some embodiments of the invention, the PCD structure may have aninterstitial mean free path in the range from about 0.05 micron to about1.3 microns, in the range from about 0.1 micron to about 1 micron, or inthe range from about 0.5 micrometers to about 1 micron; and the standarddeviation of the mean free path may be in the range from about 0.05micron to about 1.5 microns, or in the range from about 0.2 micron toabout 1 micron.

In some embodiments of the invention, the PCD structure may have a meandiamond grain contiguity of at least about 60 percent, in the range from60.5 percent to about 80 percent, in the range from 60.5 percent toabout 77 percent, or in the range from 61.5 percent to about 77 percent.In one embodiment of the invention, the PCD structure may have a meandiamond grain contiguity of at most about 80 percent.

In some embodiments of the invention, the PCD structure may have atransverse rupture strength of at least about 900 MPa, at least about950 MPa, at least about 1,000 MPa, at least about 1,050 MPa, or even atleast about 1,100 MPa.

In some embodiments of the invention, the substrate may be formed ofcemented carbide, such as cobalt-cemented tungsten carbide, or thesubstrate may comprise PCD material, or the substrate may be a compositecompact element comprising cemented carbide and PCD material. In oneembodiment of the invention, the PCD structure may be brazed to afurther PCD structure, and in one embodiment, the PCD structure may bemore thermally stable than the further PCD structure.

In some embodiments of the invention, the substrate may includesuperhard particles such as diamond particles dispersed within it. Inone embodiment, the substrate may include diamond particles, the contentof which may be in the range from about 20 volume percent to about 60volume percent.

In some embodiments of the invention, the PCD structure may exhibit nosubstantial structural degradation or deterioration of hardness orabrasion resistance after exposure to a temperature above about 400degrees centigrade or in the range from about 750 degrees centigrade toabout 800 degrees centigrade, or even in the range from about 760degrees centigrade to about 810 degrees centigrade.

In one embodiment, the PCD structure may be substantially free ofmaterial capable of functioning as solvent/catalyst for diamond. In someembodiments, there may be less than about 5 volume percent, less thanabout 2 volume percent, less than about 1 volume percent or less thanabout 0.5 volume percent of solvent/catalyst for diamond in the PCDstructure. In some embodiments, the PCD structure may be at leastpartially porous, or substantially the entire PCD structure may beporous.

In some embodiments of the invention, the PCD structure may have anoxidation onset temperature of at least about 800 degrees centigrade, atleast about 900 degrees centigrade or even at least about 950 degreecentigrade.

In some embodiments of the invention, the PCD structure may not besubstantially entirely porous and may have a mean Young's modulus of atleast about 900 GPa, at least about 950 GPa, at least about 1,000 GPa;and the transverse rupture strength is at least about 1,000 MPa, atleast about 1,100 Mpa, at least about 1,400 MPa, at least about 1,500MPa, or even at least about 1,600 MPa.

In one embodiment of the invention, PCD structure may include a fillermaterial comprising a ternary carbide of the general formula: Mx M′y Czwherein; M is at least one metal selected from the group consisting ofthe transition metals and the rare earth metals; M′ is a metal selectedfrom the group consisting of the main group metals or metalloid elementsand the transition metals Zn and Cd; x is from 2.5 to 5.0; y is from 0.5to 3.0; and z is from 0.1 to 1.2.

In some embodiments, the PCD structure may include a filler materialcomprising a tin-based inter-metallic or ternary carbide compound formedwith a metallic solvent/catalyst for diamond. In one embodiment, themetallic solvent/catalyst material for diamond may comprise cobalt.

In one embodiment of the invention, the shear strength of the bondbetween the PCD structure and the substrate may be greater than about100 MPa. In some embodiments, the shear strength of the bond between thePCD structure and the substrate may be in the range from about 100 MPato about 500 MPa, in the range from about 100 MPa to about 300 MPa, orin the range from about 200 MPa to about 300 MPa.

In some embodiments of the invention, the PCD structure may comprise atleast about 90 volume percent inter-bonded diamond grains having a meansize in the range from about 0.1 microns to 25 microns, in the rangefrom about 0.1 micron to 20 microns, in the range from about 0.1 micronto about 15 microns, in the range from about 0.1 microns to about 10microns, or in the range from about 0.1 micron to about 7 micron. In oneembodiment, the PCD structure may comprise a diamond content in therange from about 90 to about 99 volume percent of the PCD structure, andin one embodiment, the PCD structure may comprise at least 92 volumepercent diamond.

In one embodiment of the invention, the PCD structure may comprisediamond grains having a multi-modal size distribution. In someembodiments, the PCD structure may comprise bonded diamond grains havingthe size distribution characteristic that at least about 50 percent ofthe grains have mean size greater than about 5 microns, and at leastabout 20 percent of the grains have mean size in the range from about 10to about 15 microns.

In some embodiments of the invention, the PCD structure may be made by amethod including forming a plurality of diamond grains into anaggregated mass and sintering them in the presence of a solvent/catalystmaterial for diamond, the sintering including subjecting the aggregatedmass and the solvent/catalyst material to a temperature sufficientlyhigh for the solvent/catalyst to melt and to a pressure of greater than6.0 GPa, at least 6.2 GPa, at least about 6.5 GPa, at least about 7 GPaor at least about 8 GPa.

In some embodiments of the invention, the PCD structure may comprise atleast two portions, each portion being formed of PCD material havingdifferent microstructure, composition or diamond particle sizedistribution, or combination of these, and different properties, such asstrength or Young's modulus. In some embodiments, at least one portionmay comprise diamond particles having a multi-modal size distributionwith mean particle size in the range from about 5 microns to about 20microns, or in the range from about 5 microns to 15 about microns.

In one embodiment of the invention, the PCD composite compact elementmay be suitable for a drill bit for boring into the earth, such as arotary shear-cutting bit for use in the oil and gas drilling industry.In one embodiment, the PCD composite compact element may comprise acutting element for a rolling cone, hole opening tool, expandable tool,reamer or other earth boring tools.

An embodiment of the invention provides a polycrystalline diamond (PCD)composite compact element, comprising a PCD structure bonded to asubstrate; the PCD structure being substantially free of materialcapable of functioning as solvent/catalyst for diamond and having a meanYoung's modulus of at least about 800 GPa, at least about 850 GPa, or atleast about 870 GPa.

An embodiment of the invention provides a tool comprising an embodimentof a PCD composite compact element according to the invention, the toolbeing for cutting, milling, grinding, drilling, earth boring, rockdrilling or other abrasive applications, such as the cutting andmachining of metal.

A method of making an embodiment of a PCD composite compact elementaccording to the invention is provided, the method including providing aPCD structure, treating the PCD structure to remove filler material frombetween diamond grains and create pores, crevices or irregularities at aboundary of the PCD structure; and brazing the PCD structure to asubstrate at the boundary. The method is an aspect of the invention.

In one version of the method, pores, crevices or irregularities may beformed on a surface of the PCD structure by means of treating the PCDstructure with acid. In one embodiment, the pores, crevices orirregularities may have a mean size substantially the same as the meansize of the interstices between the diamond grains, and in someembodiments, the mean size may be at least about 2 microns or at leastabout 5 microns, and at most about 10 microns.

DRAWINGS

Non-limiting embodiments will now be described with reference to theaccompanying drawings of which:

FIG. 1A shows a schematic perspective view of an embodiment of a PCDcomposite compact element, and FIG. 1B shows schematic longitudinalcross-section view of the embodiment of the PCD composite compactelement shown in FIG. 1A.

FIG. 2, FIG. 3, FIG. 4, FIG. 5 and FIG. 6 show drawings of schematiclongitudinal cross-section views of embodiments of PCD composite compactelements.

FIG. 7 shows a perspective view of a rotary drill bit for boring intothe earth.

FIG. 8 shows an image of a PCD polished section, showing calculatedlines indicating diamond-to-diamond contact.

FIG. 9, FIG. 10 and FIG. 11 show graphs of number of grains versus grainsize for examples of multimodal size distributions of the diamond grainswithin embodiments of polycrystalline diamond structures.

FIG. 12 shows a schematic side view of an apparatus for measuring thetransverse rupture strength of a specimen.

The same reference numbers refer to the same features in all drawings.

DETAILED DESCRIPTION OF EMBODIMENTS

As used herein, a “catalyst material for diamond”, also referred to as“solvent/catalyst for diamond”, is a material that is capable ofpromoting the nucleation, growth or inter-bonding of diamond grains at apressure and temperature at which diamond is thermodynamically stable.Catalyst materials for diamond may be metallic, such as cobalt, iron,nickel, manganese and alloys of these, or non-metallic.

As used herein, “polycrystalline diamond” (PCD) material comprises amass of diamond grains, a substantial portion of which are directlyinter-bonded with each other and in which the content of diamond is atleast about 80 volume percent of the material. In one embodiment of PCDmaterial, interstices between the diamond gains may be at least partlyfilled with a binder material comprising a catalyst for diamond. As usedherein, “interstices” or “interstitial regions” are regions between thediamond grains of PCD material. In embodiments of PCD material,interstices or interstitial regions may be substantially or partiallyfilled with a material other than diamond, or they may be substantiallyempty. As used herein, a “filler” material is a material that wholly orpartially fills pores, interstices or interstitial regions within astructure, such as a polycrystalline structure. Thermally stableembodiments of PCD material may comprise at least a region from whichcatalyst material has been removed from the interstices, leavinginterstitial voids between the diamond grains. As used herein, a“thermally stable PCD” structure is a PCD structure at least a part ofwhich exhibits no substantial structural degradation or deterioration ofhardness or abrasion resistance after exposure to a temperature aboveabout 400 degrees centigrade.

With reference to FIG. 1A and FIG. 1B, an embodiment of a PCD compositecompact element 100 may comprise a thermally stable PCD structure 120bonded to the substrate 130 by means of a bond material in the form of abond layer 140 between the PCD structure 120 and the substrate 130. Inone version of the embodiment, the PCD structure 120 may besubstantially free of material capable of functioning assolvent/catalyst for diamond. In another version of the embodiment, thePCD structure 120 may include non-metallic solvent/catalyst for diamond.

With reference to FIG. 2, an embodiment of a PCD composite compactelement 100 may comprise a first PCD structure 122 bonded to a secondPCD structure 124 by means of a bond material in the form of a bondlayer 140 between the first PCD structure 122 and the second PCDstructure 124. The first PCD structure 122 may be more thermally stablethan the second PCD structure 124. The second PCD structure 124 may beintegrally bonded to a cemented carbide substrate 130.

With reference to FIG. 3, an embodiment of a PCD composite compactelement 100 may comprise a first PCD structure 122 bonded to a secondPCD structure 124 by means of a bond material in the form of a bondlayer 140 between the first PCD structure 122 and the second PCDstructure 124. The second PCD structure 124 may be bonded by means of abond material in the form of a bond layer 142 between the second PCDstructure 124 and the substrate 140.

With reference to FIG. 4, an embodiment of a PCD composite compactelement 100 may comprise a first PCD structure 122 bonded to a secondPCD structure 124 by means of a bond material in the form of a bondlayer 140 between the first PCD structure 122 and the second PCDstructure 124. The second PCD structure 124 may not be bonded orotherwise joined to a cemented carbide substrate.

With reference to FIG. 5, an embodiment of a PCD composite compactelement 100 may comprise a PCD structure 120 bonded to the substrate 130by means of a bond material in the form of a bond layer 140, and thesubstrate 130 may include diamond particles 132 dispersed within it.

“Young's modulus” is a type of elastic modulus and is a measure of theuniaxial strain in response to a uniaxial stress, within the range ofstress for which the material behaves elastically. A preferred method ofmeasuring the Young's modulus E is by means of measuring the transverseand longitudinal components of the speed of sound through the material,according to the equation E=2ρ.C_(T) ²(1+υ), whereυ=(1−2(C_(T)/C_(L))²)/(2−2(C_(T)/C_(L))²), C_(L) and C_(T) arerespectively the measured longitudinal and transverse speeds of soundthrough it and ρ is the density of the material. The longitudinal andtransverse speeds of sound may be measured using ultrasonic waves, as iswell known in the art. Where a material is a composite of differentmaterials, the mean Young's modulus may be estimated by means of one ofthree formulas, namely the harmonic, geometric and rule of mixturesformulas as follows: E=1/(f₁/E₁+f₂/E₂)); E=E₁ ^(f1)+E₁ ^(f2); and E=f₁E₁+f₂ E₂; in which the different materials are divided into two portionswith respective volume fractions of f₁ and f₂, which sum to one.

With reference to FIG. 6, an embodiment of a PCD composite compactelement 100 may comprise a PCD structure 120 bonded to a cementedcarbide substrate 130 by means of a bond material in the form of a bondlayer 140, in which the PCD structure 120 may comprise a first portion122 integrally formed with a second portion 124 and the first and secondportions may have different microstructure, composition or diamondparticle size distribution, or combination of these, and differentproperties, such as strength or Young's modulus.

In the embodiments described with reference to FIG. 1A, FIG. 1B, FIG. 2,FIG. 3, FIG. 4, FIG. 5 and FIG. 6, the bond material may comprise orconsist of a braze alloy material and the bond layer 140 may be a brazelayer. In one embodiment, the bond material may comprise or consist ofan epoxy material for bonding or joining ceramic materials.

With reference to FIG. 7, an embodiment of an earth-boring rotary drillbit 200 of the present invention includes, for example, a plurality ofcutting elements 100 as previously described herein with reference toFIG. 1. The earth-boring rotary drill bit 200 includes a bit body 202that is secured to a shank 204 having a threaded connection portion 206(e.g., a threaded connection portion 206 conforming to industrystandards such as those promulgated by the American Petroleum Institute(API)) for attaching the drill bit 200 to a drill string (not shown).The bit body 202 may comprise a particle-matrix composite material or ametal alloy such as steel. The bit body 202, may be secured to the shank204 by one or more of a threaded connection, a weld, and a braze alloyat the interface between them. In some embodiments, the bit body 202 maybe secured to the shank 204 indirectly by way of a metal blank orextension between them, as known in the art.

The bit body 202 may include internal fluid passageways (not shown) thatextend between the face 203 of the bit body 202 and a longitudinal bore(not shown), which extends through the shank 204 the extension 208 andpartially through the bit body 202. Nozzle inserts 224 also may beprovided at the face 203 of the bit body 202 within the internal fluidpassageways. The bit body 202 may further include a plurality of blades216 that are separated by junk slots 218. In some embodiments, the bitbody 202 may include gage wear plugs 222 and wear knots 228. A pluralityof PDC cutting elements 100 of one or more of embodiments as previouslydescribed herein may be mounted on the face 203 of the bit body 202 incutting element pockets 212 that are located along each of the blades216. In other embodiments, PDC cutting elements 100 as previouslydescribed with reference to FIG. 1, FIG. 2, FIG. 3, FIG. 4, FIG. 5, FIG.6 or any other embodiment of a PDC cutting element of the presentinvention, may be provided in the cutting element pockets 212.

The cutting elements 100 are positioned to cut a subterranean formationbeing drilled while the drill bit 200 is rotated under weight on bit(WOB) in a bore hole about centreline L200.

In the field of quantitative stereography, particularly as applied tocemented carbide material, “contiguity” is understood to be aquantitative measure of inter-phase contact. It is defined as theinternal surface area of a phase shared with grains of the same phase ina substantially two-phase microstructure (Underwood, E. E, “QuantitativeStereography”, Addison-Wesley, Reading Mass. 1970; German, R. M. “TheContiguity of Liquid Phase Sintered Microstructures”, MetallurgicalTransactions A, Vol. 16A, July 1985, pp. 1247-1252). As used herein,“diamond grain contiguity” κ is a measure of diamond-to-diamond contactor bonding, or a combination of contact and bonding within PCD material,and is calculated according to the following formula using data obtainedfrom image analysis of a polished section of PCD material:

κ=100*[2*(δ−β)]/[(2*(δ−β))+δ], where δ is the diamond perimeter, and βis the binder perimeter.

As used herein, the “diamond perimeter” is the fraction of diamond grainsurface that is in contact with other diamond grains. It is measured fora given volume as the total diamond-to-diamond contact area divided bythe total diamond grain surface area. The binder perimeter is thefraction of diamond grain surface that is not in contact with otherdiamond grains. In practice, measurement of contiguity is carried out bymeans of image analysis of a polished section surface. The combinedlengths of lines passing through all points lying on alldiamond-to-diamond interfaces within the analysed section are summed todetermine the diamond perimeter, and analogously for the binderperimeter.

FIG. 8 shows an example of a processed SEM image of a polished sectionof a PCD structure, showing the boundaries 360 between diamond grains320. These boundary lines 360 were calculated by the image analysissoftware and were used to measure the diamond perimeter and subsequentlyfor calculating the diamond grain contiguity. The non-diamond regions340, which may be filled interstices or voids, for example, areindicated as dark areas. The binder perimeter was obtained from thecumulative length of the boundaries 360 between the diamond 320 and thenon-diamond or interstitial regions 340.

FIG. 9, FIG. 10 and FIG. 11 show non-limiting examples of multimodalgrain size distributions of diamond grains within embodiments of PCDstructures, for the purpose of illustration. As used herein, a“multimodal” size distribution of a mass of grains is understood to meanthat the grains have a size distribution with more than one peak 400,each peak 400 corresponding to a respective “mode”. Multimodalpolycrystalline bodies may be made by providing more than one source ofa plurality of grains, each source comprising grains having asubstantially different average size, and blending together the grainsor grains from the sources. Measurement of the size distribution of theblended grains may reveal distinct peaks corresponding to distinctmodes. When the grains are sintered together to form the polycrystallinebody, their size distribution may be further altered as the grains arecompacted against one another and fractured, resulting in the overalldecrease in the sizes of the grains. Nevertheless, the multimodality ofthe grains may still be clearly evident from image analysis of thesintered article.

The size of grains is expressed in terms of equivalent circle diameter(ECD). As used herein, the “equivalent circle diameter” (ECD) of aparticle is the diameter of a circle having the same area as a crosssection through the particle. The ECD size distribution and mean size ofa plurality of particles may be measured for individual, unbondedparticles or for particles bonded together within a body, by means ofimage analysis of a cross-section through or a surface of the body.Unless otherwise stated herein, dimensions of size, distance, perimeter,ECD, mean free path and so forth relating to grains and intersticeswithin PCD material, as well as the grain contiguity, refer to thedimensions as measured on a surface of, or a section through a bodycomprising PCD material and no stereographic correction has beenapplied. For example, the size distributions of the diamond grains asshown in FIG. 9, FIG. 10 and FIG. 11 were measured by means of imageanalysis carried out on a polished surface, and a Saltykov correctionwas not applied.

In one embodiment of the invention, the PCD structure may comprise afirst portion formed of a PCD material comprising diamond grains havingat least three modes in the multimodal size distribution as shown inFIG. 9, and a second portion formed of a PCD material comprising diamondgrains having at least four-modes multimodal size distribution as shownin FIG. 10, the mean size of the grains in the first portion beingsubstantially less than that in the second portion, and the first andsecond portions of the PCD structure being integrally formed with eachother. The PCD structure may be brazed to the substrate with the secondportion of the PCD structure proximate the substrate and the firstportion of the PCD structure remote from the substrate.

In one embodiment of the invention, the PCD structure may comprise afirst portion formed a PCD material comprising diamond grains having twomodes in the multimodal size distribution as shown in FIG. 11, and asecond portion formed of a PCD material comprising diamond grains havingat least three modes in the multimodal size distribution as shown inFIG. 9, the first and second portions of the PCD structure beingintegrally formed with each other. The PCD structure may be brazed tothe substrate with the second portion of the PCD structure proximate thesubstrate and the first portion of the PCD structure remote from thesubstrate.

In some embodiments, the PCD structure may be as taught in PCTpublication number WO2009/027948, which discloses a PCD structurecomprising a diamond phase and a filler material, the filler materialcomprising a ternary carbide of the general formula: Mx M′y Cz wherein;M is at least one metal selected from the group consisting of thetransition metals and the rare earth metals; M′ is a metal selected fromthe group consisting of the main group metals or metalloid elements andthe transition metals Zn and Cd; x is from 2.5 to 5.0; y is from 0.5 to3.0; and z is from 0.1 to 1.2.

In some embodiments, the PCD structure may be as taught in PCTpublication number WO2009/027949, which discloses PCD composite materialcomprising inter-grown diamond grains and a filler material, the fillermaterial comprising a tin-based inter-metallic or ternary carbidecompound formed with a metallic solvent/catalyst. The use of CoSn mayfacilitate PCD sintering at high-pressure high temperature conditions atwhich the temperature is between about 1,300 and about 1,450 degreescentigrade and the pressure is between about 5.0 and about 5.8 GPa. Insome embodiments, substantially all of the cobalt may be removed fromthe PCD structure prior to brazing the structure to a substrate.

The homogeneity of the microstructure may be characterised in terms ofthe combination of the mean thickness of the interstices between thediamonds, and the standard deviation of this thickness. The homogeneityor uniformity of a PCD structure may be quantified by conducting astatistical evaluation using a large number of micrographs of polishedsections. The distribution of a filler phase or of pores within the PCDstructure may be easily distinguishable from that of the diamond phaseusing electron microscopy and can be measured in a method similar tothat disclosed in EP 0 974 566 (see also WO2007/110770). This methodallows a statistical evaluation of the average thicknesses orinterstices along several arbitrarily drawn lines through themicrostructure. The mean binder or interstitial thickness is alsoreferred to as the “mean free path”. For two materials of similaroverall composition or binder content and average diamond grain size,the material that has the smaller average thickness will tend to be morehomogenous, as this indicates a finer scale distribution of the binderin the diamond phase. In addition, the smaller the standard deviation ofthis measurement, the more homogenous is the structure. A large standarddeviation indicates that the binder thickness varies widely over themicrostructure and that the structure is not uniform.

As used herein, the “interstitial mean free path” within apolycrystalline material comprising an internal structure includinginterstices or interstitial regions, such as PCD, is understood to meanthe average distance across each interstitial between different pointsat the interstitial periphery. The average mean free path is determinedby averaging the lengths of many lines drawn on a micrograph of apolished sample cross section. The mean free path standard deviation isthe standard deviation of these values. The diamond mean free path isdefined and measured analogously.

In measuring the mean value and deviation of a quantity such as graincontiguity, or other statistical parameter measured by means of imageanalysis, several images of different parts of a surface or section areused to enhance the reliability and accuracy of the statistics. Thenumber of images used to measure a given quantity or parameter may be atleast about 9 or even up to about 36. The number of images used may beabout 16. The resolution of the images needs to be sufficiently high forthe inter-grain and inter-phase boundaries to be clearly made out. Inthe statistical analysis, typically 16 images are taken of differentareas on a surface of a body comprising the PCD material, andstatistical analyses are carried out on each image as well as across theimages. Each image should contain at least about 30 diamond grains,although more grains may permit more reliable and accurate statisticalimage analysis.

In some embodiments, the PCD structure may be as taught in PCTpublication number WO2007/020518, which discloses polycrystallinediamond a polycrystalline diamond abrasive element comprising a finegrained polycrystalline diamond material characterised in that it has aninterstitial mean-free-path value of less than 0.60 microns, and astandard deviation for the interstitial mean-free-path that is less than0.90 microns. In one embodiment, the polycrystalline diamond materialmay have a mean diamond grain size of from about 0.1 micron to about10.5 microns.

In some embodiments, the PCD structure may be manufactured using amethod including sintering of diamond grains in an ultra-high pressureand temperature (HPHT) process in the presence of a solvent/catalystmaterial for diamond and then removing solvent/catalyst material frominterstices within the PCD structure. Catalyst material may be removedfrom the PCD table using methods known in the art such as electrolyticetching, acid leaching and evaporation techniques. In some embodiments,a masking or passivating medium may be introduced into pores within thePCD structure.

Solvent/catalyst material may be introduced to an aggregated mass ofdiamond grains for sintering in various ways known in the art. One wayincludes depositing metal oxide onto the surfaces of a plurality ofdiamond grains by means of precipitation from an aqueous solution priorto forming their consolidation into an aggregated mass. Such methods aredisclosed in PCT publications numbers WO2006/032984 and alsoWO2007/110770. Another way includes preparing or providing metal alloyincluding a catalyst material for diamond, such as cobalt-tin alloy, inpowder form and blending the powder with the plurality of diamond grainsprior to their consolidation into an aggregated mass. The blending maybe carried out by means of a ball mill. Other additives may be blendedinto the aggregated mass.

In one embodiment, the aggregated mass of diamond grains, including anysolvent/catalyst material particles or additive material particles thatmay have been introduced, may be formed into an unbonded or looselybonded structure, which may be placed onto a cemented carbide substrate.The cemented carbide substrate may contain a source of catalyst materialfor diamond, such as cobalt. The assembly of aggregated mass andsubstrate may be encapsulated in a capsule suitable for an ultra-highpressure furnace apparatus and subjecting the capsule to a pressure ofgreater than 6 GPa. Various kinds of ultra-high pressure apparatus areknown and can be used, including belt, torroidal, cubic and tetragonalmulti-anvil systems. The temperature of the capsule should be highenough for the source of catalyst material to melt and low enough toavoid substantial conversion of diamond to graphite. The time should belong enough for sintering to be completed but as short as possible tomaximise productivity and reduce costs.

As noted previously, the PCD structure may have an oxidation onsettemperature of at least about 800 degrees centigrade. Embodiments ofsuch PCD may have superior thermal stability and exhibit superiorperformance in applications such as oil and gas drilling, wherein thetemperature of a PCD cutter element can reach several hundred degreescentigrade. Oxidation onset temperature is measured by means ofthermo-gravimetric analysis (TGA) in the presence of oxygen, as is knownin the art.

In some embodiments of the invention, the bond material may comprise ahigh shear strength epoxy resin or epoxy paste material for joiningceramic materials, for example epoxy paste under the trade name ES550™from Permabond™, or solder material. In one embodiment, the bondmaterial may comprise or consist of an organic adhesive.

In some embodiments the PCD structure may be brazed to the substrate bymeans of microwave brazing, wherein the braze material is heated bymeans of microwave energy. Brazing the PCD using an active brazematerial in a very high vacuum may result in braze strength high enoughfor the PCD compact element to be technically and economically viable.Active brazing is discussed by H. R. Prabhakara (in “Vacuum brazing ofceramics and graphite to metals”, Bangalore Plasmatek Pvt. Ltd, 129,Block-14, Jeevanmitra Colony I-Phase, Bangalore 560 078).

In some embodiments, the braze alloy may have a melting onsettemperature, at which the alloy begins to melt, of at most about 1,050degrees centigrade, at most about 1,000 degrees centigrade or at mostabout 950 degrees centigrade. Such embodiments may have the advantage ofpermitting a PCD structure to be brazed to a substrate at a temperaturesufficiently low that thermally-induced degradation the PCD may bereduced or avoided. The process of brazing PCD to a substrate may becarried out in a substantially inert atmosphere that inhibits oxidation,which may have the advantage of resulting in a stronger braze bond.

In one embodiment, the braze alloy may comprise an element that readilyreacts with carbon to form carbide, and in one embodiment, the brazealloy may be a reactive braze alloy, which may effectively wet thesurface of diamond.

In one embodiment, the braze alloy may contain Ti, which may effectivelywet the surface of the diamond. In some embodiments, the braze alloy maycontain Cu, Ni, Ag or Au, which may effectively wet a cemented carbidesubstrate. One type of reactive braze alloy may modify the surface ofthe diamond operative to make it more readily wettable. Examples of thistype of reactive braze alloys may comprise Mo, W, Ti, Ta, V and Zr. Insome embodiments, the braze alloy may comprise or consist essentially ofTi, Cu and Ag, also referred to as “TiCuSil” braze alloys, which maycomprise a eutectic composition of Ag and Cu, as well as an amount ofTi. For example, the weight ratio of Ti to Cu to Ag may be4.5:26.7:68.8, or the ratio of Ti to Cu to Ag may be 10.0:25.4:64.6, orthe ratio of Ti to Cu to Ag may be 15.0:24.0:61.0. In one embodiment,the braze alloy may comprise about 63.00% Ag, about 32.25% Cu and about1.75% Ti, and may be available under the trade name of Cusil™ ABA. Inone embodiment, the braze alloy may comprise about 70.5% Ag, about 26.5%Cu and about 3.0% Ti, available under the trade name of CB4,

Braze alloys having a high strength may include Cu, alloys comprising Niand Cr alloys, and brazes containing high percentages of elements suchas Pd and similar high strength materials, and Cr-based active brazes.In one embodiment, the braze alloy may comprise or consist essentiallyof Ni, Pd and Cr. In some embodiments, the ratio of the weight ratio ofPd to Ni may be in the range from about 0.4 to about 0.8. In oneembodiment, the braze alloy may comprise Ni, Pd, Cr, B and Si, and inone embodiment, the weight ratio of Ni to Pd to Cr to B to Si may beabout 50:36:10.5:3:0.5, or the weight ratio of Ni to Pd to Cr to B to Simay be about 57:30:10.5:2.4. Braze alloy material comprising Ni, Pd, Cr,B may be obtained under the trade name Palnicro™ 36M from WESGO Metals™.In one embodiment, the braze alloy may comprise Ag, Cu, Ni, Pd and Mn,and in one embodiment, the weight ratio of Ag to Cu to Ni to Pa and Mnmay be about 25:37:10:15 and 13. Such a braze alloy may be availableunder the trade name PALNICUROM™ 10. In one embodiment, the braze alloymay comprise about 64% iron and about 36% nickel, which may be referredto as Invar. In one embodiment, the braze material may comprise asubstantially unalloyed metal such as Co. In some embodiments, the brazealloy may comprise at least one element selected from the groupconsisting of Cr, Fe, Si, C, B, P, Mo, Ni, Co, W, and Pd. One example ofa suitable braze alloy may be available from Metglas™ under the tradename MBF 15.

In some embodiments, the braze alloy may comprise at least one of Cu, Agor Au, and in some embodiments, the braze alloy may further comprise atleast one of Ti, V, Cr, Mn, Zr, Nb, Mo, Hf, Ta, W or Re. For example,the braze alloy may contain Au and Ta, or the braze alloy may containAg, Cu and Ti. In some embodiments, the braze material may comprise atleast one of Fe, Co, Ni or Mn.

In one embodiment of the invention, the method may include coating asurface of the PCD structure to prepare it form brazing, and thenbrazing the PCD structure to the substrate. Examples of coatings forthis purpose and methods of applying them are described in U.S. Pat.Nos. 5,500,248; 5,647,8781; 5,529,805 and PCT patent applicationpublication number 2008/142657.

In one embodiment, the braze layer may contain dispersed ceramicparticles, and in one embodiment, the ceramic particles may comprise acarbide material, such as silicon carbide, or a super-hard material suchas diamond. In some embodiments, the ceramic particles may have meansize of less than about 20 microns or less than about 10 microns. Insome embodiments of the invention, the presence of the ceramic particlesin the braze layer may to strengthen it and may reduce the likelihood ofthe composite compact element failing as a result of the braze.

Embodiments of the invention may be used as gauge trimmers on othertypes of earth-boring tools, such as cones of roller cone drill bits,reamers, mills, bi-centre bits, eccentric bits, coring bits andso-called hybrid bits that include both fixed cutters and rollingcutters.

Grain contiguity may be determined from SEM images by means of imageanalysis software. In particular, software having the trade nameanalySIS Pro from Soft Imaging System® GmbH (a trademark of Olympus SoftImaging Solutions GmbH) may be used. This software has a “SeparateGrains” filter, which according to the operating manual only providessatisfactory results if the structures to be separated are closedstructures. Therefore, it is important to fill up any holes beforeapplying this filter. The “Morph. Close” command, for example, may beused or help may be obtained from the “Fillhole” module. In addition tothis filter, the “Separator” is another powerful filter available forgrain separation. This separator can also be applied to colour- andgrey-value images, according to the operating manual.

As used herein, “transverse rupture strength” (TRS) is measured bysubjecting a specimen in the form of a disc to a load applied at threepoints, two applied on one side of the specimen and one applied on theopposite side, and increasing the load at a loading rate until thespecimen fractures. Such a measurement may also be referred to as athree-point bending test, and has been described by Borger et al.(Borger, A., P. Supansic and R. Danner, “The ball on three balls testfor strength testing of brittle discs: stress distribution in the disc”,Journal of the European Ceramic Society, 2002, volume 22, pp.1425-1436). With reference to FIG. 12, a specimen 510 of the material tobe tested is placed between a load ball 520 and two support balls 530,and supported by a guide body 570. The load ball 520 is supported by astamp 560, which is supported laterally and guided by a guide body 570,and a chock 580 is disposed between respective parts of the guide body570 and the stamp 560 and establishes a proximity limit to the movementof the stamp 560 with respect to the guide body 570. A punch 550 abutssupport balls 530, which are disposed between the punch 550 and thespecimen 510. An axial load 540 is applied to the punch 550 causing theload ball 520 and the support balls 530 to be urged against the specimen510 from opposite sides. The load is increased at a certain loading ratefrom a lower limit until evidence of fracture is observed in thespecimen 510. As a non-limiting example, an Instron™ 5500R universaltesting machine having a load cell of 10 KN may be used for measuringtransverse rupture strength as described above. The loading rate may beabout 0.9 mm/min. The transverse rupture strength σ in MPa is calculatedas f(F).F/t², where F is the measured load, in Newtons, at which thespecimen begins to fracture, t is the thickness of the specimen and f(F)is a dimensionless constant dependent on the load and the material beingtested. In the case of PCD, f(F)=1.620211−0.0082×(F−3000)/1000.

The specimen in the form of a round disc for use in the TRS measurementdescribed above is prepared as follows. A PCD construction comprising aPCD structure joined to a substrate is provided, the outer diameter ofwhich is ground to 16 mm or 19 mm. The substrate is removed, leaving afree-standing the PCD disc, which is then lapped to a thickness in therange from about 1.30 mm to about 2.00 mm. The PCD disc may be treatedin acid to remove some or substantially all of the material in theinterstices between the diamond grains.

The K1C toughness of a PCD disc is measured by means of a diametralcompression test, which is described by Lammer (“Mechanical propertiesof polycrystalline diamonds”, Materials Science and Technology, volume4, 1988, p. 23.) and Miess (Miess, D. and Rai, G., “Fracture toughnessand thermal resistances of polycrystalline diamond compacts”, MaterialsScience and Engineering, 1996, volume A209, number 1 to 2, pp. 270-276).

Embodiments of the invention are described in more detail with referenceto the examples below, which are not intended to limit the invention.

Example 1

A PCD disc having thickness of about 2.2 millimetres and diameter ofabout 16 mm was provided using a known high-pressure high temperaturemethod. The substrate to which the PCD was bonded during the sinteringstep was removed by grinding, leaving an un-backed, free-standing PCDdisc. The PCD comprised coherently bonded diamond grains having amulti-modal size distribution with mean equivalent circle diameter ofabout 9 microns. Microstructural data for the PCD is shown in Table 1,in which the mean grain size is expressed in terms of equivalent circlediameter and the values shown in parentheses are the respective standarddeviations.

TABLE 1 Mean diamond grain size, Diamond content Filler mean freeDiamond grain microns of PCD, volume % path, microns contiguity, % 9.0(4.0) 91 (0.4) 0.6 (0.5) 62.0 (1.7)

The PCD disc was then treated (leached) in acid to remove substantiallyall of the cobalt solvent/catalyst material throughout the entire PCDstructure.

Several additional discs, each having a diameter of about 19 mm, weremade as described above and subjected to a range of tests to measuremechanical properties. Mechanical properties of the PCD discs after acidtreatment are shown in Table 2, in which the values shown in parenthesesare the respective standard deviations. It was found that the TRS of thePCD disc decreased from about 1,493 MPa before leaching to about 1,070MPa after leaching (i.e. by approximately 28%), and the Young's modulusdecreased from about 1,025 GPa to about 864 GPa (i.e. by about 15% to16%).

TABLE 2 Transverse rupture K₁C toughness, Young's strength, MPa MPa ·m^(1/2) modulus, GPa 1,070 (100) 6.8 (0.2) 864 (14)

A cobalt-cemented tungsten carbide substrate having substantially thesame diameter as the 16 mm PCD disc was provided. A foil of active brazematerial having thickness of about 100 microns was sandwiched betweenthe PCD disc and the substrate to form a pre-compact element assembly.The braze material comprised 63.00% Ag, 32.25% Cu and 1.75% Ti, and isavailable under the trade name of Cusil™ ABA. Prior to brazing, the PCDdisc was ultrasonically cleaned, and both the tungsten carbide substrateand the braze foil was slightly ground and then ultrasonically cleaned.

The pre-compact element assembly was subjected to heat treatment in avacuum. The temperature was increased to 920 degrees centigrade over 15minutes, held at this level for 5 minutes and then reduced to ambienttemperature over about 8 to 9 hours. A vacuum of at least 10⁻⁵ millibarwas maintained during the heat treatment. Care was taken to avoid orminimise the amount of oxygen and other impurities in the furnaceenvironment. Furthermore, a furnace with convection heating and lowtemperature gradients was used because the components to be brazed andthe braze material should all reach the desired temperature inrelatively short time.

The molten braze material was found to infiltrate into the PCD disc to adepth in the range from 10 to 20 microns, leaving a braze layer of about50 microns to about 80 microns between the PCD and WC substrate. Theshear strength of the braze bond was measured to be in the range from110 MPa to 150 MPa.

A control PCD composite compact element that had not been detached fromits original substrate and had not been treated in acid was provided forcomparison. The brazed and control composite compacts were processed toform respective cutter elements and subjected to a wear test involvingusing them to machine a granite block mounted on a vertical turretmilling apparatus. The test result is expressed in terms of the depth ofthe wear scar at the cutting edge of the compact element after a givennumber of passes. The smaller the wear scar depth, the better. After 55passes, the wear scar depth of the compact element was about 3.5 mm,compared to about 4 mm for the control element.

Example 2

A PCD compact element having a diameter of 16 mm was prepared asdescribed in Example 1, except that a different braze material was used.The braze material comprised 70.5% Ag, 26.5% Cu and 3.0% Ti, availableunder the trade name of CB4, and the brazing step was carried out at atemperature of 950 degrees centigrade. The molten braze material wasfound to infiltrate into the PCD disc to a depth in the range from 5 to10 microns. The shear strength of the braze bond was found to be in therange from 110 MPa to 150 MPa.

The brazed compact element was subjected to a wear test as described inExample 1. After 55 passes, the wear scar depth of the compact elementwas about 2 mm.

Example 3

Example 1 was repeated, except that the PCD disc comprised coherentlybonded diamond grains having a multi-modal size distribution with meanequivalent circle diameter of about 4.6 micrometres. Microstructuraldata for the PCD is shown in table 3.

TABLE 3 Mean diamond grain size, Diamond content Filler mean freeDiamond grain microns of PCD, volume % path, microns contiguity, % 4.6(1.3) 90.2 (0.3) 0.4 (0.3) 58.7 (1.7)

The PCD disc was then treated in acid to remove substantially all of thecobalt solvent/catalyst material within the interstices between thediamond grains, as is well known in the art.

Several additional discs, each having a diameter of about 19 mm, weremade as described above and subjected to a range of tests to measuremechanical properties. Key mechanical properties of the PCD after acidtreatment are shown in table 4.

TABLE 4 Transverse rupture K₁C toughness, Young's strength, MPa MPa ·m^(1/2) modulus, GPa 1,200 (120) 7.8 (0.8) Not measured

The molten braze material was found to infiltrate into the PCD disc to adepth in the range from about 10 microns to 20 about microns. The shearstrength of the braze bond was measured to be in the range from 110 MPato 150 MPa.

The brazed PCD compact element was subjected to a further wear test,wherein the compact element was used to mill a block of granite. After acutting length of at least 6,000 millimetres, no failure due to thebraze joint was observed.

Example 4

PCD composite compact elements each comprising a layer of PCD materialhaving a diameter of 16 mm, in which the mean diamond grain size wasabout 9 microns and the content of cobalt was about 9.0 volume % wereprovided by sintering the diamond grains onto respective cementedcarbide substrates at a pressure of about 5.5 GPa and a temperature ofabout 1400 degrees centigrade. Microstructural data for the PCD is shownin Table 5, in which the mean grain size is expressed in terms ofequivalent circle diameter.

TABLE 5 Mean diamond grain size, Diamond content Filter mean freeDiamond grain microns of PCD, volume % path, microns contiguity, % 9.0(4.0) 91 (0.4) 0.6 (0.5) 62.0 (1.7)

The substrates were removed from the PCD layers, which were then treatedin acid to remove substantially all of the cobalt filler material.Inductively coupled plasma (ICP) analysis confirmed the residualpresence of about 2 weight %, which is about 1.1 volume % Co in the PCDstructure. The residual cobalt may have been trapped withinsubstantially closed pores of the PCD structure. Key mechanicalproperties of the PCD discs after acid treatment are shown in Table 6,in which the values shown in parentheses are the respective standarddeviations. The oxidation onset temperature of the PCD in this cutterwas measured to be 870 degrees centigrade.

TABLE 6 Transverse rupture K₁C toughness, Young's strength, MPa MPa ·m^(1/2) modulus, GPa 831 5.6 (0.3) 844

A treated PCD structure was brazed onto a cemented tungsten carbidesubstrate using an alloy comprising 70.5 weight % Ag, 26.5 weight % Cuand 3.0 weight % Ti, a formulation available under the trade name CB4from BrazeTec™. The brazing was carried out in a vacuum furnace, under avacuum of 10⁻⁶ mbar, at 950 degrees centigrade for about 5 minutes. Theshear strength of the braze bond between the PCD structure and thesubstrate was about 287 MPa at room temperature and about 224 MPa at 300degrees centigrade.

A control PCD composite compact element that had not been detached fromits original substrate and had not been treated in acid was provided forcomparison. The brazed compact and the control composite compacts wereprocessed to form respective cutter elements and subjected to a weartest involving using them to machine a granite block mounted on avertical turret milling apparatus. The test result can be expressed interms of the depth of the wear scar or area of wear scar at the cuttingedge of the compact element after a given number of passes. The smallerthe wear scar depth or area, the better. After 55 passes, the wear scararea of the example compact element was about 5.2 mm², compared to about18.9 mm² for the control element.

Example 5

PCD structures in the form of discs having a diameter of 16 mm and inwhich the diamond grains had a mean size of about 9 microns weremanufactured by sintering the grains onto respective substrates at apressure of about 6.8 GPa and a temperature of about 1,400 degreescentigrade. Microstructural data for the PCD is shown in Table 7, inwhich the mean grain size is expressed in terms of equivalent circlediameter.

TABLE 7 Mean diamond grain size, Diamond content Filler mean freeDiamond grain microns of PCD, volume % path, microns contiguity, % 9 (4)91.4 (0.4) 0.7 (0.6) 63.0 (1.5)

The substrates were removed and the PCD structures were treated in acidto remove substantially all of the cobalt filler material. Keymechanical properties of the PCD discs after acid treatment are shown inTable 8, in which the values shown in parentheses are the respectivestandard deviations.

TABLE 8 Transverse rupture K₁C toughness, Young's strength, MPa MPa ·m^(1/2) modulus, GPa 983 Not measured 927

A treated PCD disc was brazed onto a cemented tungsten carbide substrateusing an alloy comprising 70.5 weight % Ag, 26.5 weight % Cu and 3.0weight % Ti, a formulation available under the trade name CB4 fromBrazeTec™, as described in Example 4.

The brazed compact was processed to form a cutter element and subjectedto a wear test involving using it to machine a granite block mounted ona vertical turret milling apparatus. The test result can be expressed interms of the depth of the wear scar or area of wear scar at the cuttingedge of the compact element after a given number of passes. The smallerthe wear scar depth or area, the better. After 55 passes, the wear scararea of the example compact element was about 3.26 mm², compared toabout 18.9 mm² for the control element described in Example 4.

Example 6

PCD structures in the form of discs having a diameter of 16 mm and inwhich the diamond grains had a mean size of about 4 microns and whichcontained about 10 volume % cobalt, were manufactured by sintering thegrains onto respective substrates at a pressure of about 5.5 GPa and atemperature of about 1,400 degrees centigrade. Microstructural data forthe PCD is shown in Table 9, in which the mean grain size is expressedin terms of equivalent circle diameter.

TABLE 9 Mean diamond grain size, Diamond content Filler mean freeDiamond grain microns of PCD, volume % path, microns contiguity, % 4.2(1.6) 89.2 (0.5) 0.4 (0.3) 65 (1)

The substrate was removed and the PCD structure was treated in acid toremove substantially all of the cobalt filler material. Key mechanicalproperties of the PCD disc after acid treatment are shown in Table 8, inwhich the values shown in parentheses are the respective standarddeviations.

TABLE 10 Transverse rupture K₁C toughness, Young's strength, MPa MPa ·m^(1/2) modulus, GPa 1,058 6.9 846

The treated PCD disc was brazed onto a cemented tungsten carbidesubstrate using an alloy comprising 70.5 weight % Ag, 26.5 weight % Cuand 3.0 weight % Ti, a formulation available under the trade name CB4from BrazeTec™, as described in Example 4.

A control PCD composite compact element that had not been detached fromits original substrate and had not been treated in acid was provided forcomparison. The brazed and control composite compacts were processed toform respective cutter elements and subjected to a wear test involvingusing them to machine a granite block mounted on a vertical turretmilling apparatus. The test result can be expressed in terms of thedepth of the wear scar or area of wear scar at the cutting edge of thecompact element after a given number of passes. The smaller the wearscar depth or area, the better. After 55 passes, the wear scar area ofthe example compact element was about 3.33 mm², compared to about 4.09mm² for the control element.

Example 7

PCD structures in the form of discs, in which the diamond grains had amean size of about 4 microns and containing about 10 volume % cobalt,were manufactured by sintering the grains onto respective substrates ata pressure of about 6.8 GPa and a temperature of about 1,400 degreescentigrade. Microstructural data for the PCD is shown in Table 11, inwhich the mean grain size is expressed in terms of equivalent circlediameter.

TABLE 11 Mean diamond Diamond content Diamond grain grain size, of PCD,volume Filler mean free contiguity, microns percent path, micronspercent 4.3 (1.2) 89 (1) 1 (1.6) 57.8 (1)

The substrates were removed and the PCD structures were treated in acidto remove substantially all of the cobalt filler material.

A treated PCD was brazed onto a cemented tungsten carbide substrateusing an alloy comprising 70.5 weight % Ag, 26.5 weight % Cu and 3.0weight % Ti, a formulation available under the trade name CB4 fromBrazeTec™, as described in Example 4.

The brazed composite compact was processed to form a utter element andsubjected to a wear test involving using it to machine a granite blockmounted on a vertical turret milling apparatus. The test result can beexpressed in terms of the depth of the wear scar or area of wear scar atthe cutting edge of the compact element after a given number of passes.The smaller the wear scar depth or area, the better. After 55 passes,the wear scar area of the example compact element was about 3.28 mm²,compared to about 4.09 mm² for the control element described in Example6.

Example 8

PCD discs were provided and treated as described in Example 4, and atreated PCD disc was brazed onto a cemented tungsten carbide substrateusing a braze alloy comprising 86.0 weight % Cu, 12.0 weight % Mn and2.0 weight % Ni at 1050 degrees centigrade for about 5 minutes invacuum. The braze material was available as 21/80 from BrazeTec™.

The brazed composite compact was processed to form a cutter element andsubjected to a wear test involving using it to machine a granite blockmounted on a vertical turret milling apparatus. The test result can beexpressed in terms of the depth of the wear scar or area of wear scar atthe cutting edge of the compact element after a given number of passes.The smaller the wear scar depth or area, the better. After 55 passes,the wear scar area of the example compact element was about 3.65 mm²,compared to about 18.9 mm² for the control element described in Example4.

Example 9

PCD discs were provided and treated as described in Example 4, and atreated disc was glued onto a cemented tungsten carbide substrate usingPermabond ES550™ epoxy resin at about 100 degrees centigrade for about 2hours.

The brazed and control composite compact was processed to form a cutterelement and subjected to a wear test involving using it to machine agranite block mounted on a vertical turret milling apparatus. The testresult can be expressed in terms of the depth of the wear scar or areaof wear scar at the cutting edge of the compact element after a givennumber of passes. The smaller the wear scar depth or area, the better.After 55 passes, the wear scar area of the example compact element wasabout 4.44 mm², compared to about 18.9 mm² for the control elementdescribed in Example 4.

Example 10

A PCD disc was provided and treated as described in Example 4, and wasbrazed onto a cemented tungsten carbide substrate using a braze alloycomprising 68.8 weight % Ag, 26.7 weight % Cu and 4.5 weight % Ti alloyat about 950 centigrade for about 5 minutes in vacuum. The brazematerial was available under the product name Ticusil™ from Wesgo™.

Example 11

A PCD disc was provided and treated as described in Example 4, and wasbrazed onto a cemented tungsten carbide substrate using a braze alloycomprising 68.8 weight % Ag, 26.7 weight % Cu and 4.5 weight % Ti alloyat about 950 centigrade for about 5 minutes in an argon atmosphere. Thebraze material was available under the product name Ticusil™ fromWesgo™. The shear strength of the braze bond was about resultant cuttingelement had bond shear strength of 215 MPa at room temperature.

Known PCD composite compact elements comprising PCD structures brazed tosubstrates have lacked commercially success, particularly in harshapplications such as drilling into rock, especially in the oil and gasdrilling industry. Such applications require cutter compact elementscapable of maintaining extreme abrasion resistance and high strength athigh temperatures experienced in use, typically in excess of 600 degreescentigrade. While wanting not to be bound by theory, brazing of PCD tocarbide may give rise to high internal stresses within the compactelement proximate the braze interface, resulting in cracking of the PCDand/or the substrate or the delamination of the PCD even before thecompact element is used to bore into rock. Embodiments of PCD compositecompact elements according to the invention, particularly embodiments inwhich the PCD structure is thermally stable may be economically viableand commercially successful.

Embodiments of the invention in which the PCD structure has a meanYoung's modulus of at least about 800 GPa may better retain itsmechanical integrity and robustness after being bonded to the substrate.If the Young's modulus is substantially less than about 800 GPa, or ifthe transverse rupture strength is substantially less than about 900MPa, the PCD structure may not be able to cut rock efficiently and maywear too rapidly. Embodiments of PCD that have a homogeneousmicrostructure, characterised in terms of the combination of theinterstitial mean free path and the standard deviation of theinterstitial mean free path, may have enhanced resistance to mechanicaland thermal stress and shock, as may be experience when brazing the PCDto a substrate and using the composite compact to degrade or bore intorock.

Embodiments having the combination of the high contiguity and/or highhomogeneity and/or reduced content of metallic solvent/catalyst withinthe PCD structure, and a size distribution comprising at least two orthree peaks or modes, have the advantage of bonding particularly wellusing conventional brazing. Embodiments may exhibit superior durabilityover prior art cutter elements comprising PCD brazed to a substrate.

Embodiments of the invention may have the advantage that the strengthwith which the PCD structure is bonded to the substrate may besubstantially enhanced. In particular, embodiments in which the PCDstructure is brazed to the substrate and in which the PCD structurecontains braze material to a depth of at least about 2 microns from aninterface with the braze layer may have exhibit a particularly enhancedstrength of bonding. Consequently, the mechanical properties and workinglife of such embodiments may be enhanced, particularly when used to boreinto rock.

Embodiments of the invention in which the shear strength of the bondbetween the PCD structure and the substrate is at least about 100 MPaand at most about 500 MPa, may have the advantage that conventionalbrazing methods may be adequate.

Embodiments of the invention in which the PCD structure is thermallystable may have the advantage that the PCD structure better retains itsstructural integrity and key mechanical properties after being bonded tothe substrate by means of a method involving heating the PCD structure,such as brazing. Embodiments of the invention in which the PCD structurehas a filler comprising carbide or inter-metallic compounds may haveenhanced thermal stability and better retain key mechanical propertiesafter being bonded to the substrate, such as by brazing.

Embodiments of the invention in which the substrate comprises cementedcarbide and includes diamond particles dispersed in it may have enhancedmechanical robustness, particularly fracture resistance.

Embodiments of the invention in which the PCD structure comprises atleast 90 volume percent diamond grains having a mean size of at mostabout 10 microns may be especially advantageous. Embodiments of PCDstructures having a multi-modal diamond grain size distribution havesufficient strength to retain better their mechanical integrity and keyproperties after bonding to the substrate, such as by brazing.

Embodiments of the invention may have the advantage that the compositionof the PCD structure, particularly the composition of the fillermaterial, may be selected with fewer constraints associated with thecomposition of the substrate. PCD structures having desirableproperties, particularly high thermal stability, can be made separatelyfrom the substrate and then bonded to the substrate using known brazingmaterials and methods, thereby improving the performance of the PCD toolwithout incurring substantial additional costs.

Although the foregoing description of PCD composite compact element,tools, manufacturing methods and various applications contain manyspecific details, these should not be construed as limiting the scope ofthe invention, but merely as providing illustrations of some exampleembodiments. Similarly, other embodiments of the invention may bedevised which do not depart from the spirit or scope of the presentinvention. The scope of the invention is indicated and limited only bythe appended claims and their legal equivalents, rather than by theforegoing description. All additions, deletions, and modifications tothe invention, as disclosed herein, which fall within the meaning andscope of the claims are to be embraced.

1. A PCD composite compact element comprising a substrate, a PCDstructure bonded to the substrate, and a bond material bonding the PCDstructure to the substrate; the PCD structure being thermally stable andhaving a mean Young's modulus of at least about 800 GPa, the PCDstructure having an interstitial mean free path of at least about 0.05microns and at most about 1.5 microns; the standard deviation of themean free path being at least about 0.05 microns and at most about 1.5microns.
 2. A PCD composite compact element as claimed in claim 1, inwhich the bond material is a braze alloy in the form of a braze layerbetween the PCD structure and the substrate.
 3. A PCD composite compactelement as claimed in claim 2, in which the braze alloy has a meltingonset temperature of at most about 1,050 degrees centigrade and containsat least one element selected from the group consisting of Ti, V, Cr,Mn, Zr, Nb, Mo, Hf, Ta, W and Re.
 4. A PCD composite compact element asclaimed in claim 1, in which the bond material comprises an epoxymaterial for joining ceramic materials.
 5. A PCD composite compactelement as claimed in claim 3, in which the substrate comprises PCDmaterial.
 6. A PCD composite compact element as claimed in claim 3, inwhich there is less than about 5 volume percent of solvent/catalyst fordiamond in the PCD structure.
 7. A PCD composite compact element asclaimed in claim 2, in which the PCD structure is at least partiallyporous.
 8. A PCD composite compact element as claimed in claim 3, inwhich the PCD structure has a mean diamond grain contiguity of at leastabout 60 percent.
 9. A PCD composite compact element as claimed in claim3, in which the PCD structure has transverse rupture strength of atleast about 900 MPa.
 10. A PCD composite compact element as claimed inclaim 2, in which the substrate includes diamond particles dispersedwithin it.
 11. A PCD composite compact element as claimed in claim 3, inwhich the PCD structure is not substantially entirely porous and has amean Young's modulus of at least about 900 GPa, and a transverse rupturestrength of least about 1,000 MPa.
 12. A PCD composite compact elementas claimed in claim 2, secured to a drill bit or other earth boringtool.
 13. A PCD composite compact element comprising a PCD structurebonded to a substrate by means of a bond material; the PCD structurebeing thermally stable and having a mean Young's modulus of at leastabout 800 GPa and a mean diamond grain contiguity greater than about 60percent.
 14. A PCD composite compact element as claimed in claim 13, inwhich the bond material is a braze alloy in the form of a braze layerbetween the PCD structure and the substrate.
 15. A PCD composite compactelement as claimed in claim 14, in which the braze alloy has a meltingonset temperature of at most about 1,050 degrees centigrade and containsat least one element selected from the group consisting of Ti, V, Cr,Mn, Zr, Nb, Mo, Hf, Ta, W and Re.
 16. A PCD composite compact element asclaimed in claim 13, in which the bond material comprises an epoxymaterial for joining ceramic materials.
 17. A PCD composite compactelement as claimed in claim 15, in which there is less than about 5volume percent of solvent/catalyst for diamond in the PCD structure. 18.A PCD composite compact element as claimed in claim 14, in which the PCDstructure is at least partially porous.
 19. A PCD composite compactelement as claimed in claim 15, secured to a drill bit or other earthboring tool.
 20. A PCD composite compact element as claimed in claim 15,in which the PCD structure has an interstitial mean free path in therange from about 0.05 micron to about 1.5 microns; and the standarddeviation of the mean free path is in the range from about 0.05 micronto about 1.5 microns.
 21. A PCD composite compact element as claimed inclaim 15, in which the PCD structure has transverse rupture strength ofat least about 900 MPa.
 22. A PCD composite compact element as claimedin claim 14, in which the substrate includes diamond particles dispersedwithin it.
 23. A PCD composite compact element as claimed in claim 14,in which the PCD structure is not substantially entirely porous and hasa mean Young's modulus of at least about 900 GPa, and a transverserupture strength of least about 1,000 MPa.
 24. A PCD composite compactelement comprising a PCD structure bonded to a substrate by means of abraze layer comprising braze alloy; the PCD structure being thermallystable and containing braze material.
 25. A PCD composite compactelement as claimed in claim 24, in which the braze alloy has a meltingonset temperature of at most about 1,050 degrees centigrade and containsat least one element selected from the group consisting of Ti, V, Cr,Mn, Zr, Nb, Mo, Hf, Ta, W and Re.
 26. A method of making a PCD compositecompact element as claimed in claim 25, the method including providing aPCD structure, treating the PCD structure to remove filler material frombetween diamond grains and create pores, crevices or irregularities at aboundary of the PCD structure; and brazing the PCD structure to asubstrate at the boundary.